Hydrocarbon lubricating oil composition



United States Patent 3,248,361 HYDROCARBON LUBRICATING OIL COMPOSITION Ralph I. Gottshall, Fox Chapel, and John G. Peters, Irwin,

Pa., and Howard W. Swain, Chatsworth, Califi, assignors to Gulf Research & Development Company, Pittsburgh, Pa., a corporation of Delaware No'Drawing. Original application Aug. 10, 1959, Ser.

No. 832,453. 1965, Ser. No. 438,064

9 Claims. (Cl. 25242.7)

This application is a division of our copending application Serial No. 832,453, now abandoned, filed August 10, 1959.

This invention relates to new, oil-soluble, resinous addition products. More particularly, the invention relates to addition products of olefin oxides and sulfide-modified condensation products of substituted phenols and low molecular weight aliphatic aldehydes, or partial metal salts of such condensation products, and to hydrocarbon oil compositions containing these resinous addition products.

In the lubrication of two-cycle engines, straight or uncompounded hydrocarbon lubricating oils are normally employed as cylinder lubricants in order to minimize deposition of soot, ash, or carbonaceous deposits in the com bustion zone as a result of the combustion and/ or thermal decomposition of the lubricating oil. However, in the operation of some two-cycle engines, for example, two-cycle gas engines that employ as a fuel a hydrocarbon gas such as methane or propane, especially those of relatively high power ratings, difficulties have been encountered in the use of ordinary, uncompounded hydrocarbon lubricating oils in that dense, carbonaceous combustion deposits have been found to form in the vicinity of the combustion cham bers of such engines, especially in the combustion chamber intake ports and to some extent in the exhaust ports, whereby proper engine functioning is adversely affected.

It has now been found that the problem of combustion chamber deposits arising from the combustion of hydrocarbon lubricating oils employed to lubricate twocycle engines, as well as problems of bearing corrosion and oil detergency in these or other hydrocarbon oils, can be .alleviated by incorporating in the oil a small proportion of an addition product of an olefin oxide containing 2 to 4 carbon atoms per molecule and either a I uct we prefer has the general formula:

I XL

where R is a straight or branched chain alkyl group containing 4 to 12 carbon atoms, preferably para to the hydroxyl group of the phenolic nucleus, where Z is hydrogen, methylol, ethylol, propylol, or butylol, n is 1 to Divided and this application Mar. 8,-

9, at least one X group per molecule isa group having the general formula:

y being 1 to 3, and the other X groups in the molecule are groups having the formula:

butylphenol and formaldehyde, and these materials are' therefore preferred. However, there can be prepared and used in accordance with the present invention, addition products of other olefin oxides, such as ethylene oxide and 1,2-butylene oxide, and the sulfide-modified condensation products of other aldehydes such as acetaldehyde, propionaldehyde, and butyraldehyde and other substituted phenols such as n-butylphenol, sec-butylphenol, tart-butylphenol, n-amylphenol, di-tert-amylphenol, hexylphenol, heptylphenol, n-octylphenol, nonylphenol, decylphenol, triisobutylphenol, wax phenols and the like, and/or the partial salts of such condensation products and other metals such as sodium, potassium, barium, strontium, calcium, zinc, and magnesium. In general, the addition products disclosed herein will produce an improvement in the hydrocarbon oils disclosed herein when employed in proportions in the range of about 0.1

to 10 percent, and preferably 0.5 to 5 percent by weight, but other proportions can be used.

The exact manner in which the addition products disclosed herein function to reduce the combustion deposits resulting from the combustion of lubricating oils in twocycle engines is not known. However, it is presumed that the addition products disclosed herein function at least in part to modify the nature of the combustion deposits so that they are more easily removed from the combustion chamber region by way of the exhaust. This presumption is based on the fact that deposits formed from oils containing the addition products disclosed herein under conditions substantially similar to those in the combustion chamber of a two-cycle gas engine have been found not only to be reduced in amount, but also to occur in the form of a soft, white, low-density, friable material, rather than in the form of a dense, hard, black material as is the case when no addition product is employed. v

The addition products disclosed herein are preferably prepared by reacting the desired olefin oxide with the desired partial salt in the proportion range of about 0.25 to 1 mole of olefin oxide for each phenolic nucleus per mole of the sulfide-modified condensation product or its partial salt, but larger and smaller proportions of olefin oxide can be used. For example, there can be used as little as 0.15 mole of olefin oxide and there can be used up to the maximum number of moles of olefin oxide that will react with each phenolic nucleus in a' mole of the sulfidemodified condensation product or partial salt. The maximum proportion of olefin oxide that will react with the sulfide-modified condensation product or partial metal salt depends primarily on the nature of the olefin oxide and tion.

upon the number of phenolic acidic hydrogen atoms that are present in the condensation product or partial salt. Thus, an olefin oxide having a relatively low molecular weight, such as ethylene oxide, will normally react with a given sulfide-modified condensation product or salt in greater proportions than an olefin oxide having a somewhat higher molecular Weight. The proportion of olefin oxide that will react with the sulfide-modified condensation product or salt can also be affected somewhat by the presence of alkylol groups in the ortho positions of the terminal phenolic nuclei, as olefin oxides can also add to the hydroxyl groups of alkylol radicals. Usually the proportion of olefin oxide that will react with the sulfidemodified condensation products and the partial salts disclosed herein will be under about 2 moles per mole of phenolic nucleus per mole of sulfide-modified condensation product or partial salt, but no difficulty is encountered by the use of an excess of olefin oxide, as the unreacted excess is easily separated from the addition product by distillation or the like.

The olefin oxides disclosed herein can add to the sulfidemodified condensation products and partial salts disclosed herein at ambient atmospheric conditions, but we prefer to employ elevated temperatures to accelerate the reac- Although the sulfide-modified condensation products and partial salts can be reacted as such with the olefin oxide, we prefer to carry out the reaction with the condensation product or partial salt in the form of a solution in a light hydrocarbon oil or naphtha solvent.- After addition of the olefin oxide to the reaction mixture is complete, the mixture is preferably heated to a temperature sufiicient to reflux the lower boiling component or components of the mixture. By way of example, a temperature of 130 F. to 150 F. is sufficient when'propylene oxide is the olefin oxide. Lower temperatures, for example, 95 F. to 110 F., can be employed when ethylene oxide is used and correspondingly higher temperatures, for example, 160 F. to 180 F., can be used when the olefin oxide is butylene oxide.

When the addition reaction is complete, usually in less than about two hours, the specific time depending on the nature of the reactants and the reaction conditions, the temperature is raised above the temperature maintained during refluxing and above the boiling point of water, say to 300 F., in order to strip off unreacted olefin oxide and in order to dry the product.

The partial salts of the sulfide-modified condensation products disclosed herein, from which the olefin oxide addition products are obtained, are prepared by condensing the desired substituted phenol, aliphatic aldehyde, and an alkali metal, ammonium, or Group II metal sulfide, or hydrogen sulfide itself in an aqueous alkaline medium. We prefer not to employ hydrogen sulfide as such because of the difficulties involved in handling a gaseous reactant. Rather, we prefer to employ a water-soluble sulfide that is capable of producing hydrogen sulfide under the conditions of condensation, such as the alkali metal, ammonium, or alkaline earth metal sulfides incuding the monoas well as poly-sulfides. Suitable sulfidemodified condensation products have been obtained with sodium monosulfide, ammonium sulfide, and with calcium monosulfide, but monoand poly-sulfides of other metals such as potassium, lithium, barium, and strontium, can be used. The metal and ammonium sulfides disclosed not only serve as a source of sulfur in the reaction but also furnish the desired alkaline reaction medium. When a Group II metal partial salt is desired, it is not necessary that a sulfide of the Group II metal be employed directly in the condensation reaction. Instead, the condensation reaction can be carried out with, for example, sodium monosulfide, and the Group II metal partial salt can be formed by metathesis of the alkali metal partial salt and a water-soluble salt such as a chloride or nitrate of the desired Group II metal, e.g., calcium, magnesium, or zinc chlorides.

It will be understood that when a metal sulfide is employed in the condensation reaction, the product obtained will be in the form of a partial metal salt. When the sulfide-modified condensation product is desired as such, this material can conveniently be obtained by treatment of the corresponding partial sodium salt with a strong mineral acid such as hydrochloric acid.

Normally we prefer to condense at least about 1 mole of formaldehyde and about 0.05 to about 1.8 equivalents of the sulfide with each 2 moles of substituted phenol. However, greater proportions of aldehyde and sulfide can be used, as any excess unreacted materials can easily be removed as such by distillation, washing, and/ or by filtration. It may be noted that while we prefer for reasons of economy to employ no more sulfide than will enter into the condensation reaction, the use of greater proportions of sulfide will not prevent formation of a partial metal salt. The use of the aldehyde in proportions of at least 1 mole per 2 moles of substituted phenol is important so as to minimize any tendency toward formation of oil-insoluble resins rather than the permanently thermoplastic, oil-soluble, resinous materials employed in this invention. The use of at least 0.05 equivalent of sulfide is important as the sulfur contributes significantly to the combustion deposit inhibiting characteristics of the ultimate reaction products disclosed herein.

In carrying out the condensation reaction, the substituted phenol and the aldehyde should not be permitted to condense in the absence of the sulfide. Except for this precaution, the reactants can be admixed and reacted in any order. Thus, the sulfide and the substituted phenol can be admixed and reacted and the aldehyde can be subsequently reacted, or the sulfide and aldehyde can be admixed and reacted and the substituted phenol can be subsequently reacted, or the sulfide, aldehyde, and substituted phenol can be admixed and reacted together. The condensation reaction can take place spontaneously to some extent at ambient atmospheric conditions of temperature and pressure, but moderately elevated temperatures are preferred in order to facilitate the reaction. When the substituted phenol and metal sulfide are reacted alofie, the initial reaction temperature can be raised as high as 400 F. However, when the aldehyde is introduced into the reaction, the reaction temperature is preferably maintained below the point at which excessive volatilization of aldehyde will occur. For example, when formaldehyde is employed, the reaction is preferably maintained below 200 to 210 F., although higher temperatures can be employed when a closed system is utilized.

The condensation reaction is usually carried out in the presence of added water. When formaldehyde is the aldehyde employed in the condensation reaction, this material will normally be employed in the form of formalin (a 37 percent solution in water), and the water contained therein will serve effectively as the water added to the reaction mixture. However, whether or not an aqueous aldehyde is employed, it is convenient to introduce the metal sulfide into the reaction mixture in the form of an aqueous solution or slurry.

Although the aforementioned condensation reaction can be carried out solely in an aqueous medium, it is preferred to employ a light hydrocarbon oil or a volatile hydrocarbon solvent as a diluent. There is then obtained, after drying, a concentrate of the intermediate sulfide-modified condensation product or partial salt in solution in the hydrocarbon liquid. This concentrate forms a desired medium for the final reaction with olefin oxide.

The preparation of the addition products useful in compositions of this invention is further illustrated by reference to the following specific examples.

EXAMPLE I Into a reaction vessel equipped with a condenser and means for agitating, heating, and cooling was charged 412 phenol and 500 parts by weight of a light lubricating oil, a typical sample of which had a viscosity of 76 SUS at 100 F. These materials were heated to a temperaoil, was determined after removal of the volatile solvent to have the following general formula:

ture of 160 F. in order to dissolve all the substituted 5 phenol in the lubricating oil. There was then added 192 parts by weight of a 50 percent by weight aqueous solution of technical grade, 75 percent purity, calcium monosulfide (1.0 mole). The mirttlure was heatedfto 08H" 08H" 08H" 180 F. with stirring and held at at temperature or one hour. Thereafter, the mixture was cooled to 160 F., 10 Z n 13 an j5, h an averagla 5 of and 170 parts by weight of a 37 percent by weight aqueous t 6 .average tom 9 Su stltuents per m0 ecu e are solution of formaldehyde (2 moles) was slowly added sodlum the Temamder bemg Z f and an average with Stirring. The mixture was agitated at 180 F. for of 2 of the average total of 6 X groups per molecule twohours. The mixture was then dried by heating to 15 f CH2 S CH2 m remamqer bemg. i a temperature of 300 F. and filtered. There was then y groups speqtrqp m exammatlon [added an additional 500 Parts by weightqof the light of the above material also 1nd1cated the presence of a lubricating oil described above. At this Point 58 Parts methylol substituent in the free ortho positlons of at by weight of propylene oxide (1 mole) was added and least.some.of the termmal phFlllohc substltuenls 9 the allowed to react with the aforementioned filtered product i g j i i t produced as mdlcated at a-temperature of 98 F. for one-half hour, after-which a e o owmg c arac ens the temperature was raised until refluxing occurred, i.e., from 130 F. to 150 F., and refluxing was continued Actual x255 313 for approximately one hour. The temperature was then indicated raised to about 300 F. in order to strip off, any unreacted propylene oxide. The resinous product obtained M 1 ht 709 1714 had the following pwperflw slfiiitd ielliifie, 5555.153?"-":::::::::i:: 1 19.3 20.7 Gravity: API 210 np u 3924 Viscosity, SUS 1 100 F. 1547 The lubricating oil solution of the reaction product 210 F. 87.9 prepared as indicated above was next metathesized by Color, ASTM Union 3.25 admixture with 75 parts by weight of calcium chloride Sulfur, B: percent 0-6 (0.65 mole) dissolved in water and heating to a temper- Calcium: percent 1- ature of 280 F.- to remove water. The resulting product EXAMPLE H was then filtered to remove salt. There was then added Into a reaction vessel there was charged 412 parts by E 3 a zh of ar hght gf f gg v o1 escri e a ove. 0 1s InlX ure ere was a e Weight 1110169 of P Y Y P Q and parts by weight (0.5 mole) of propylene oxide, which was 500 P i y Welght of the Same 11gb? lubncatmg 011 40 allowed to react at a temperature of 98 F. for one-half P y 111 Example These mammals were heated to hour. The mineral oil solution of the addition product a temperature of 160 F. until all of the phenol was disthus Prepared the f ll i properties: 1 solved in the lubricating oil. There was then added to o the mixture 230 parts by weight of a percent by t API weight aqueous solution of technical grade, percent Vlscoslty; SUS: purity, sodium monosulfide (0.9 mole). The mixture 45 2047 was agitated and heated to a temperature of 320 F. for 210 103-4 one hour after which it was cooled to F. There- Color ASTM Unlon after, parts by weight (two moles) of a 37 percent Percent by weight aqueous solution of formaldehyde was added 50 Calcmm' Percent L1 and the mixture was heated with agitation at 170 F. In addition to the materials described above there were for one hour, unreacted formaldehyde being removed by also prepared a number of other addition products in distillation. Amaterial prepared essentially in accordance accordance with the procedure described in Example II with the above-indicated procedure, except for the use above. The make-up of the products of these embodiof a volatile hydrocarbon solvent instead of lubricating 55 rnents is indicated in the following table:

Table A Example Example Example Example Example Example III IV v VI v11 VIII Make-up, moles:

Octylphenol 2. 0 2. 0 2. 0 2. 0 2. 0 2. 0 Sodlum sulfide.-- 0. 9 0.9 0. 5 0. 05 0. 05 0. 9 aaaaaa 92 92 3-2 9:. 92. Propyleneoxide 1:3 0:8 1:0 0. 15 0.22 210 piggi rg l n 011, g 904 904 906 904 904- 904 .%I 19. 7 20. 3 20. 5 23. 0 23. 1 19. 2 100 1, 547 1,282 2, 047 833 700 2,181 210 87.9 85.3 103.4 70.5 67.4 89.4 Flash, 00, F 310 390 385 375 390 385 B, 0. 62 0. 61 3% .1 0.16 1.19 eacmr pmenijjjj "r55 "ifi' 1: 10 0:27 3:32 Sullated residue, percen 5. l5 5. 09 4. 29 0. 91 0. 77 4. 23

Still other examples of addition products that can be prepared in accordance with the procedure of Example II are indicated in the following table:

EXAMPLE XI A sodium sulfide-modified octylphenol-formaldehyde condensation product was prepared using the reactant proportions and essentially the same procedure described in Example 11, except that toluene was employed as a diluent during the condensation reaction instead of a lubricating oil. When the condensation reaction was complete, toluene and Water Were removed by distillation. The product was taken up in benzene and filtered through Celite. A portion of a benzene solution of the filtered condensation product was acidified with 10 percent aqueous hydrochloric acid. The product Was dehydrated, filtered through Celite to remove salt, washed with water until neutral, and heated to 300 F. to remove benzene. This product was determined to contain about 75 percent of a material having the general formula:

Inspection Actual Theoretical Appearance Hard, transparent resin Odor Hydrogen sulfide. Sulfur, percent"--. 3.24 3. 21 Molecular weight 737 735 The acidic product prepared as described is dissolved in toluene and reacted with 1,2-propylene oxide in a 1:1 mol ratio.

The above-indicated specific examples are illustrative only, and there can be substituted for the materials therein in the same or equivalent proportions other materials disclosed herein. For example, there can be used in lieu of the corresponding materials of the examples n-butylphenol, heptylphenol and dodecylphenol, potassium, lithium, barium, monoand poly-sulfides, barium and strontium chlorides, and ethylene and butylene oxides.

The addition products disclosed herein are excellent improvement agents for various hydrocarbon oils, and they are readily soluble in such oils. For example, the

addition products disclosed herein are soluble in lubricating oils derived from paraflinic, naphthenic or mixed base crude petroleum oils, and they can be blended with such oils in relatively large proportions. The excellent solubility of the addition products disclosed herein permits preparation of concentrated solutions thereof, as indicated in the foregoing specific examples, which concentrated solutions can be diluted With additional hydrocarbon oil in the proportions desired in the final hydrocarbon oil compositions. The addition products disclosed herein not only inhibit formation of combustion deposits When incorporated in hydrocarbon lubricating oils that are employed in the lubrication of two-cycle gas engines, but also they suppress bearing corrosion and exhibit detergent properties in crankcase lubricating oils that are employed in conventional internal combustion engines.

We have found that best results are obtained by incorporation of relatively small proportions of the addition products disclosed herein in hydrocarbon oils. The exact proportion of addition agent to be incorporated in a given hydrocarbon oil will depend primarily upon the nature of the oil itself and also upon the nature of the improvement desired. The optimum proportion of a given addition product to be added to a given hydrocarbon oil will also depend to some extent upon the effectiveness of the particular addition product chosen, as all of the addition products of the class disclosed herein are not exact functional equivalents. By way of illustration, some improvement in the detergent, bearing corrosion inhibiting and/ or combustion deposit inhibiting properties of lubricating oils can be obtained by the addition of the addition products in amounts of 0.1 percent by weight or greater, but a substantially greater improvement is obtained by the use of our addition products in lubricating oils in proportions of about 0.5 to 5 percent by weight, and proportions within this range are therefore preferred. Greater proportions, for example, up to 10 percent by Weight or more can be used in instances Where an especially large degree of improvement is needed for a given oil. Usually, no additional advantage from the standpoint of deposit inhibition, bearing corrosion inhibition and detergency will be obtained by the use of proportions greater than 10 percent.

The combustion deposit inhibiting properties of the addition products disclosed herein have been demonstrated by subjecting hydrocarbon lubricating oils con taining such addition products to the conditions of a bench scale test carried out under conditions designed to simulate those existing in the combustion zone of a twocycle gas engine. In accordance With the procedure of the test, a weighed, stainless steel tube, 20 inches long and having a inch internal diameter, equipped With a cap to permit oil and air to enter, was inserted into a 1000 Watt heating element positioned in such a manner that it was inclined 28.8 from the horizontal. A thermo couple equipped With a temperature recorder with a range of 0 to 1200 F. is attached to the shell of the stainless steel tube. The tube is then preheated to a temperature of 900 F., a temperature closely approximating the highest temperatures encountered in the cylinder intake ports of a two-cycle gas engine of a kind that has been found to promote formation of combustion deposits by combustion of the lubricating oil. A Weighed amount of the test lubricating oil is charged through the upper capped end of the stainless steel tube by means of a force-feed lubricator at the rate of 1 ml. per minute, while at the same time air is passed through the tube at the rate of 1.1 cu. ft. per minute. These test conditions are maintained for a period of four hours at which time the test is discontinued. Upon completion of the test, the stainless steel tube is allowed to cool to room temperature while continuing the flow of air so as to promote combustion of all residual oil in the tube. The tube is then weighed to determine the increase in Weight resulting from combustion deposits, and more significantly,

. cosity of 76.0 SUS at 210 F. In another specific test,

one percent by volume of the addition product of Example II was incorporated in a sample of a highly refined lubricating oil, hereinafter referred to as Base Oil B, having an API gravity of 249 and a viscosity of 69.0 SUS at 210 F. The respective test samples, here- I inafter referred to as Test Oil 1 and Test Oil 2, along with uninhibited samples of the respective base oils, were 10 defined in detail in CRC Handbook for 1946, a publication of the Coordinating Research Council, Inc. Briefly, this test involves operating a six-cylinder automotive engine at a speed of'3l50i25 r.p.m. under a load of 30:1

b.h.p. for a total of 36 hours, under prescribed operating conditions. Performance of the test oil is judged by visual inspection and rating of the engine pistons for varnish and deposits according to an ascending graduated 'scale of 0 to 10, 10 being the highest cleanliness rating. Over-all engine cleanliness is also rated on a graduated scale from 0 to 100, 100 being the highest cleanliness rating. The oil is also rated on the basis of the weight loss of a pair'of symmetrically positioned'copper-lead test bearings. The results obtained in the above-indicated subjected to the combustion deposit test described above. test were as follows:

The results obtained were as follows: Table E Test oil 7 SAE oil base Average Engine Bearing piston cleanliness wt. loss, cleanliness mg.

Engine test, CRC L-4-545:

Rating Failed, could 6. 9 89 26 not complete test.

Table C Base oil A Test oil 1 Base oil B Test oil 2 Carbon deposit test, 900 F., 4 hrs.:

Wt. of oil charged, g 230 243 222 224. Wt. of deposit, 2 1. l 0. 6 0.9 0.6. Deposit, percent of oil charged 0. 48 0. 24 0. 41 0.27. Deposit, appearance Hard, black, Soft, white, Hard, black, Soft, white,

crystalline. friable. crystalline. friable.

In addition, each of the addition products of Examples III, IV, V, and VI was added respectively in a proportion of 0.33 percent active ingredient to separate samples of -a paraflinic lubricating oil, hereinafter referred to as Base Oil C, derived from a coastal-type crude oil having a gravity of 25.4 API, a viscosity at 210 F. of 67 SUS and a viscosity index of 59, and the respective test oils, hereinafter referred to as Test Oils 3, 4, 5 and 6 were subjected to the above-indicated combustion deposit test. The results obtained in these tests are indicated in the following table:

From the foregoing test results it will be seen that the hereindescribed addition products impart detergent and bearing corrosion inhibiting properties to crankcase lubn'cants.

Other materials besides the addition products disclosed herein that are adapted to improve one or more properties of the hydrocarbon oils disclosed herein also can be added to the oils of this invention. For example, there can be added to the hydrocarbon oils disclosed herein pour point depressants, viscosity index improvers, antifoam agents, sludge inhibitors, antiwear agents, corrosion in- Table D B ase oil 0 Test oil 3 Test oil 4 Test oil 5 Test oil 6 Carbon deposit test, 900 F., 4hrs:

i1 charged, 2 222 203 21% 216 224. Deposit in tube, g. 0. 94 0. 63 0. 54 0. 67 0. 65. Degosiadpercent by wt. of oil 0.42 0.25 0.25 0.31 0.29.

c arge Deposit, appearance Hard, black.-. Soft, white Soft, white. Soft, white Soft, white.

From the test results obtained it will be seen that in every case the addition products disclosed herein reduced the amount and/or changed the appearance and nature of the deposits resulting from combustion of the test lubricating oils.

The detergent and bearing corrosion inhibiting proppylene oxide per two moles of substituted phenol, in a highly paraflinic SAE 20 motor oil base, and by subjecting the thus-obtained oil to the standard engine test procedure designated CRC L-4-545. The procedure of this test is hibitors, .dyes, other antioxidants and stabilizing agents, other detergents and the like.

Many modifications and variations of the invention as herein described will suggest themselves to those skilled in the art, and resort may be had to 'such variations and modifications without departing from the spirit or scope of the invention. Accordingly, the invention should be limited only by the scope of the claims appended hereto.

We claim:

1. A hydrocarbon oil composition comprising a major proportion of a hydrocarbon lubricating oil and containing -0.1 to 10 percent by weight of the composition of an addition product of an olefin oxide containing 2 to 4 carbon atoms per molecule and a member of the group consisting of (a) a sulfide-modified condensation product of an aliphatic aldehyde containing 1 to 4 carbon atoms per molecule and a substituted monohydric phenol that is unsubstituted in the ortho positions and that has a hydrocarbon substituent containing 4 to 18 carbon atoms and a sulfide that is capable of making available free hydrogen sulfide in the condensation reaction, said sulfide and said aldehyde being condensed in a ratio of at least about one mol of aldehyde and at least about 0.05 equivalent of sulfide for each 2 mols of said phenol, and (b) a member of the group consisting of partial salts of said sulfide-modified condensation products and alkali metals, ammonia, and Group II metals, said olefin oxide being employed in the proportion of about 0.15 to 2 mols for each phenolic nucleus in said condensation product, said addition product being formed by reaction of said olefin oxide and said condensation product at a temperature in the range of 95 to 180 F.

2. A hydrocarbon oil composition comprising a major proportion of a hydrocarbon lubricating oil and containing 0.1 to 10 percent by weight of the composition of an addition product of an olefin oxide containing 2 to 4 carbon atoms per molecule and a member of the group consisting of (a) a sulfide-modified condensation product of an aliphatic aldehyde containing 1 to 4 carbon atoms per molecule and a substituted monohydric phenol that is unsubstituted in the ortho positions and that has a hydrocarbon su'bstituent containing 4 to 18 carbon atoms, and (b) partial salts of said sulfide-modified condensation products and a member of the group consisting of alkali metals, ammonia, and Group II metals, the sulfide with which said condensation product is modified being a substance capable of making available free hydrogen sulfide in the condensation reaction.

3. A hydrocarbon oil composition comprisinga major proportion of a hydrocarbon lubricatitng oil and containing a small amount, sufficient to reduce deposits resulting from the combustion of said oil, of an addition product of an olefin oxide containing 2 to 4 carbon atoms per molecule and a member of the group consisting of (a) a sulfide-modified condensation product of an aliphatic aldehyde containing 1 to 4 carbon atoms per molecule and a substituted monohydric phenol that is unsubstituted in the ortho positions and that has a hydrocarbon substituent containing 4 to 18 carbon atoms, and (b) partial salts of said sulfide-modified condensation products and a member of the group consisting of alkali metals, ammonia, and Group II metals, the sulfide with which said condensation product is modified being a substance capable of making available free hydrogen sulfide in the condensation reaction.

4. The composition of claim 3 Where said small amount is 0.5 to 5 percent.

5. A hydrocarbon oil composition comprising a major proportion of a hydrocarbon lubricating oil, and 0.1 to percent of an addition product of an olefin oxide containing 2 to 4 carbon atoms per molecule and a partial salt of a Group II metal and an alkali metal sulfide-modified condensation product of an aliphatic aldehyde containing 1 to 4 carbon atoms per molecule and a substituted monohydric phenol that is unsubstituted in the ortho positions and that has a hydrocarbon substituent containing 4 to 18 carbon atoms.

6. A hydrocarbon oil composition comprising a major proportion of a hydrocarbon lubricating oil, and 0.1 to 10 percent of an addition product of an olefin oxide containing 2 to 4 carbon atoms per molecule and a partial salt of an alkaline earth metal and an alkali metal sulfidemo-dified condensation product of an aliphatic aldehyde containing 1 to 4 carbon atoms per molecule and a substituted monohydric phenol that is unsubstituted in the ortho positions and that has a hydrocarbon substituent containing 4 to 18 carbon atoms.

7. A hydrocarbon oil composition comprising a major proportion of a hydrocarbon lubricating oil, and 0.1 to 10 percent of an addition product of propylene oxide and a partial salt of calcium and a sodium sulfide-modified condensation product of formaldehyde and an octylphenol that is unsubstituted in the ortho positions.

8. A hydrocarbon oil composition comprising a major proportion of a hydrocarbon lubricating oil, and 0.1 to 10 percent of an addition product of an olefin oxide that contains 2 to 4 carbon atoms per molecule and a member of the group consisting of (a) a sulfide-modified condensation product having the general formula:

on on I I I] i z- X- R R n R and (b) partial salts of such sulfide-modified condensation products and a member of the group consisting of alkali metals, ammonia, and Group II metals, where R is an alkyl group containing 4 to 12 carbon atoms, where Z is selected from the group consisting of hydrogen, methylol, ethylol, propylol, and butylol, n is 1 to 9, and at least one X group per molecule is a group having the general fOrmula.

(}H S CH y on lon 1 on 8 3 17 H s n and (b) partial salts of such condensation products and an alkaline earth metal, where Z is selected from the group consisting of hydrogen and methylol, where n is 1 to 9 and at least one of said X groups per molecule is -CH S-CH the remainder of said X groups being methylene groups.

Reirerences Cited by the Examiner UNITED STATES PATENTS 2,346,826 4/1944 Cook et al. 25242.7 X 2,362,289 11/1944 Mikeska 25242.7 X 2,629,743 2/1953 Brunette et al. 260- 609 X 2,772,238 11/1956 Lowe 25248.2

DANIEL E. WYMAN, Primary Examiner.

C. F. DEES, Assistant Examiner. 

2. A HYDROCARBON OIL COMPOSITION COMPRISING A MAJOR PROPORTION OF A HYDROCARBON LUBRICATING OIL AND CONTAINING 0.1 TO 10 PERCENT BY WEIGHT OF THE COMPOSITION OF AN ADDITION PRODUCT OF AN OLEFIN OXIDE CONTAINING 2 TO 4 CARBON ATOMS PER MOLECULE AND A MEMBER OF THE GROUP CONSISTING OF (A) A SULFIDE-MODIFIED CONDENSATION PRODUCT OF AN ALIPHATIC ALDEHYDE CONTAINING 1 TO 4 CARBON ATOMS PER MOLECULE AND A SUBSTITUTED MONOHYDRIC PHENOL THAT IS UNSUBSTITUTED IN THE ORTHO POSITIONS AND THAT HAS A HYDROCARBON SUBSTITUENT CONTAINING 4 TO 18 CARBON ATOMS, AND (B) PARTIAL SALTS OF SAID SULFIDE-MODIFIED CONDENSATION PRODUCTS AND A MEMBER OF THE GROUP CONSISTING OF ALKALI METALS, AMMONIA, AND GROUP II METALS, THE SULFIDE WITH WHICH SAID CONDENSATION PRODUCT IS MODIFIED BEING A SUBSTANCE CAPABLE OF MAKING AVAILABLE FREE HYDROGEN SULFIDE IN THE CONDENSATION REACTION. 